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Calculation of Calorific Values and Relative Density from Gas


Composition (Update of ISO 6976)

Presentation · May 2019

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Calculation of Calorific Values and Relative Density
from Gas Composition (Update of ISO 6976)

Andrew Laughton
01 May 2019

American Gas Association, Operations Conference, Nashville, 2019

1 DNV GL © 01 May 2019 SAFER, SMARTER, GREENER


2. ISO 6976

▪ BS EN ISO 6976 : 2016


▪ Natural gas – Calculation of calorific values, density, relative density and Wobbe
indices from composition

▪ The ‘most’ important standard for Natural Gas energy


– Calorific value (Heating value) usually calculated from gas composition (gas
chromatography), not directly measured

▪ The 3rd edition


– 2nd edition 1995 (corrections 2005)
– Based on work done in the 1980’s
– 1st edition 1983

▪ ISO Technical Committee 193 / Sub-Committee 1 / Working Group 18

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3. Reason for update

▪ New measurements, new parameters, etc.


– New equations of state, gas constant (R), atomic weights
▪ Guidelines for proper uncertainty calculation
– All measurements should have an uncertainty
▪ Harmonization with US standards
– AGA Report no.5 “Natural Gas Energy Measurement”
– GPA Standard 2172
– API Manual of Petroleum Measurement Standards, chapter 14.5
– “Calculation of Gross Heating Value, Relative Density, Compressibility and
Theoretical Hydrocarbon Liquid Content for Natural Gas Mixtures for Custody
Transfer”

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4. Properties

▪ Gross Volumetric Calorific Value (Higher, Upper or Superior Heating Value)


– Amount of heat that would be released by the complete combustion with
oxygen of a specified quantity of gas, in such a way that the pressure (P1) at
which the reaction takes place remains constant, and all the products of
combustion are returned to the same specified temperature (T1) as that of the
reactants, all of these products being in the gaseous state except for water,
which is condensed to the liquid state at T1.
– Amount of gas in a specified volume at T2 and P2
– Reference conditions
– T1=0, 15, 20, 25 oC & 60 oF T2=0, 15, 20 oC & 60 oF (15.55 oC)
– P1=101.325 kPa P2=101.325 kPa, 14.73 psia etc.

▪ Relative Density
– (mass) density of a gas divided by the density of (dry) air of reference
composition at the same specified temperature and pressure (T2,P2)

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5. Background information

▪ Reasons behind the selection of data and methods


– Record of decisions and future improvements
▪ ISO / TR 29922 : 2017
– Natural gas – Technical support documentation for ISO 6976 3rd edition
– 104 pages

▪ All calculation methods essentially the same as in the 2nd edition


– Except for allowance of P2 being different to 101.325 kPa
– Method for Z (compressibility factor) essentially the same as in GPA 2172

▪ Unique parameter data


– 2nd edition had component parameters in several tables (to be helpful) which
meant different value could be calculated.

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6. Calorific Value

▪ Fundamental values
– kJ/mol for ideal gas at 25 oC, 101.325 kPa
– For other temperatures (T1) use ideal gas enthalpy (Ho) (from ideal gas heat
capacity equation, Cp0)
– For reactants and products
– Any effect of pressure (P1) ignored (true for ideal gas)

▪ Only methane value updated


– All other values same for 25 oC, but slightly different at other T1 (due to
different Cp0 equation)
– Uncertainty estimated and tabulated

▪ Methane was 890.63 now 890.58 kJ/mol (-0.006%)


– New measurements (standard (k=1) uncertainty 0.19 kJ/mol)

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7. Methane Calorific Value

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8. Methane CV

▪ New measurements (dated 2015) published after the standard was written

▪ Methane value is currently being reviewed by working group


– And uncertainty adjusted

▪ For completeness :-

– CV = [  Xi×CVi ] / (Z×R×T2/P2) MJ/m3


– Xi component mole fraction (not mol%)
– CVi component calorific value (kJ/mol)
– At combustion reference temperature (T1)

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9. Natural Gas Volume

▪ Compressibility factor (compression factor) Z = (P×V)/(R×T)

– Z = 1 – (P2/101.325)×[  Xi×Si ]2
– Can be considered as a 2-term pressure virial equation of state
– Z = 1 + B×P/(R×T) B second virial coefficient
– P2 90 to 110 kPa (13.05 to 15.95 psia)
– Z > 0.9 (generally natural gas Z > 0.98)
– Si component summation factors
– At metering reference temperature (T2)
– Obtained from reference equations of state (as in NIST RefProp program) or
from GERG-2008 equation of state (ISO 20765:2, AGA-8 part 2 (2017))

▪ Note issues for H2, He and Ne which have Z > 1


– Arbitrarily Si = -0.01 and uncertainty increase to allow for this

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10. Volume update

▪ Permit industry standard equation of state for Z


– E.g. GERG-2008
– Solves H2, He, Ne problem
– Addresses biases associated with H2O in the gas

– However, not so easy to do a complete uncertainty calculation


– The general 0.1 % (expanded, k=2) Uncertainty is too general

▪ Note also that 80 mol% H2 + CH4 has mixture S of zero


– which gives a zero uncertainty
– using the first order uncertainty equation given in ISO 6976

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11. Density

▪ From Z and molecular weight


– IUPAC update to atomic weights
– Now provide a range rather than a value and uncertainty
– 2007 values were taken
– H = 1.00794 (0.000035), C = 12.0107 (0.0004) (standard uncertainty)
– E.g CH4 was 16.043 now 16.04246 (-0.003%)
– Now same as GERG-2008 (AGA-8 part 2)

– Atomic weights currently being reviewed by working group


– Implications with other standards

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12. Relative Density

▪ Need density of air


– RD = density of gas / density of air (both at T2, P2)
– Update to the composition of air
– Z calculated using GERG-2008
– Expressed in terms of summation factors S (for various T2)

– Considering defining a specified fixed composition

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13. Gas Constant (R)

▪ Was 8.314510 J/mol.K


▪ Now 8.3144621 (0.0000075 uncertainty) (-0.0006%)

▪ SI due to be updated May 20, 2019


– Redefinition of base units
– Boltzmann constant, k = 1.380649×10-23 J/K Exact
– Avogadro number, NA = 6.02214076×1023 (/mol) Exact
– R = NA×k so will be Exact (no uncertainty)
– R = 8.3144626... J/mol.K

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14. Wobbe Index and Net CV

▪ A measure of the energy supplied in a flame for a given differential pressure


▪ WN = CV / √RD
– Uncertainty not √[ {u(CV)/CV}2 + 0.25×{u(RD)/RD}2 ]
– Since u(CV) and u(RD) share mole fractions and so are correlated

▪ Net CV (inferior, lower heating value)


– Standard enthalpy of vaporization of water (water stays in gas phase)
– Using IAPWS-1995 equation of state
– Wagner & Pruss, J.Phys.Chem.Ref.Data 31 p.387, 2002

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15. Conclusion

▪ ISO 6976 updated (published 2016)


– New component parameters (with uncertainty)
– Reference conditions for harmonization with USA
– Equations for uncertainty calculation

▪ ISO TC 193 / SC 1 / WG 18
– Ongoing work to review latest measurements and definitions
– Methane CV
– Atomic weights
– R

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Calculation of Calorific Values and Relative Density
from Gas Composition (Update of ISO 6976)

Andrew Laughton

andrew.Laughton@dnvgl.com

www.dnvgl.com

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